Novel tetrazole derivatives

ABSTRACT

The instant invention relates to novel tetrazole derivatives of the formula (I) wherein R 1  represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, C 1-2  haloalkoxy, methylthio, ethylthio, C 1-3  alkylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano, R 2  represents C 1-6  alkyl, C 3-6  cycloalkyl which may be optionally substituted with halogen or C 1-3  alkyl, C 1-4  haloalkyl, C 2-6  alkenyl, or phenyl which may be optionally substituted with halogen, C 1-3  alkyl, C1-4 haloalkyl, C 2-6  alkenyl, or phenyl which may be optionally substituted with halogen, C 1-3  alkyl, C 1-2  haloalkyl or nitro, m represents 0, 1 or 2, two R 1  s may be identical or different, in case m represents 2, n represents 1 or 2, Q represents one the cyclic groups which are mentioned in the specification, to intermediates and several processes for their preparation, to their use as herbicides and to novel compositions containing them.

[0001] The present invention relates to novel tetrazole derivatives, to processes for their preparation, to their intermediates, to their use as herbicides and to novel herbicidal compositions for use in paddy fields.

[0002] It has been already known that certain kinds of tetrazole derivatives show a herbicidal activity (cf. Japanese Laid-open Patent Application No. 12275/1999, No. 21280/1999 etc.). Furthermore, it has been known that certain kinds of heterocyclic derivatives show a herbicidal activity (cf. U.S. Pat. Specifications Nos. 5,834,402, 5,846,906, DE-A-19846792, WO 99/10327 etc.).

[0003] There have now been found novel tetrazole derivatives of the formula (I)

[0004] wherein

[0005] R¹ represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, C₁₋₂ haloalkoxy, methylthio, ethylthio, C₁₋₃ alkylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano,

[0006] R² represents C₁₋₆ alkyl or C₃₋₆ cycloalkyl which may be optionally substituted with halogen or C₁₋₃ alkyl, or represents C₁₋₄ haloalkyl, C₂₋₆ alkenyl, or phenyl which may be optionally substituted with halogen, C₁₋₃ alkyl, C₁₋₂ haloalkyl or nitro,

[0007] m represents 0, 1 or 2,

[0008] and the two R¹ substituents may be identical or different, in case m represents 2,

[0009] n represents 1 or 2,

[0010] Q represents one of the following groups

[0011] wherein

[0012] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each represents a hydrogen atom or methyl,

[0013] R⁹ represents a hydrogen atom, halogen, C₁₋₃ alkyl, halomethyl, methoxy or nitro,

[0014] R¹⁰ represents C₁₋₆ alkyl,

[0015] R¹¹ it represents halogen, and

[0016] k represents 1 or 2.

[0017] The compounds of the formula (I), according to the invention, can be obtained by a process wherein

[0018] a) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-1) or (Q-2):

[0019] compounds of the formula (II)

[0020] wherein

[0021] R¹, R², m and n have the same definition as aforementioned, and

[0022] T¹ represents one of the following groups

[0023] wherein

[0024] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as aforementioned,

[0025] are reacted to a rearrangement in the presence of inert solvents, and if appropriate, in the presence of a base and a cyanide, and if appropriate, in the presence of a phase-transfer catalyst,

[0026] or

[0027] b) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-6) or (Q-7) and R¹¹ in said groups represents chloro or bromo:

[0028] compounds of the formula (Ib)

[0029] wherein

[0030] R¹, R², m and n have the same definition as aforementioned, and

[0031] Q_(b) represents one of the following groups

[0032] wherein

[0033] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as aforementioned,

[0034] are reacted with a halogenating agent in the presence of inert solvents,

[0035] or

[0036] c) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-3), (Q-4) or (Q-S):

[0037] compounds of the formula (Ic)

[0038] wherein

[0039] R¹, R², m and n have the same definition as aforementioned, and

[0040] Q_(c) represents one of the following groups

[0041] wherein

[0042] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as aforementioned,

[0043] R^(11c) represents chloro or bromo,

[0044] are reacted with compounds of the formula (III)

R¹²—SH   (II)

[0045] wherein

[0046] R¹² represents the following group

[0047] R¹⁰

[0048] wherein

[0049] R⁹, R¹⁰ and k have the same definition as aforementioned,

[0050] in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent.

[0051] The tetrazole derivatives of the formula (I) provided by the present invention show stronger herbicidal activity than with the compounds described in the aforementioned prior art references.

[0052] In the formulae:

[0053] “Halogen” represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.

[0054] “Alkyl” can be straight chain or branched chain and there can be specifically mentioned, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo-, or tert-pentyl and n- or iso-hexyl.

[0055] “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. These cycloalkyls may be optionally substituted with halogen (for example, fluoro, chloro, bromo etc.), C₁₋₃ alkyl (for example, methyl, ethyl, n- or iso-propyl etc.) and in case that a plurality of substituents exist, they may be identical or different. As specific examples of such substituted cycloalkyls there can be mentioned 1-methylcyclo-propyl, 1-ethylcyclopropyl, 1-n-propylcyclopropyl, 1-methyl-2-fluorocyclopropyl, 2-methylcyclopropyl, 2-fluorocyclopropyl, 1-methyl-2,2-difluorocyclopropyl, 1-methyl-2,2-dichlorocyclopropyl, 2,2difluorocyclopropyl, 2-methylcyclopentyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,6-dimethylcyclohexyl and 2,5-dimethylcyclohexyl.

[0056] As “alkenyl” there can be mentioned, for example, vinyl, allyl, 1-methylallyl, 1,1-dimetylallyl and 2-butenyl.

[0057] “Haloalkyl” represents straight chain or branched chain alkyl, of which at least one hydrogen is substituted with halogen, and there can be mentioned, for example, C₁₋₄ alkyl substituted with 1-6 fluoro and/or chloro, specifically difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, dichloromethyl, 2-chloro-1,1,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl and 1,2,2,3,3,3-hexa-fluoropropyl.

[0058] The Haloalkyl part in “haloalkoxy” can have the same definition as the afore-mentioned “haloalkyl” and as “haloalkoxy” there can be specifically mentioned, for example, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2,2,2-trifluoroethoxy and 3-chloropropoxy.

[0059] “Alkylsulfonyl” represents an alkyl-SO₂-group, wherein the alkyl part has the above-mentioned meaning, and includes specifically methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl.

[0060] As preferred definitions in the formula (I) there can be mentioned:

[0061] R¹ preferably represents fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, C₁₋₂ haloalkoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano.

[0062] R² preferably represents C₁₋₃ alkyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl or ethyl, C₁₋₃ haloalkyl, C₂₋₄ alkenyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, ethyl, trifluoromethyl or nitro.

[0063] m preferably represents 1 or 2.

[0064] n preferably represents 1 or 2.

[0065] R⁹ preferably represents a hydrogen atom, fluoro, chloro, methyl, ethyl or tri-fluoromethyl.

[0066] R¹⁰ preferably represents methyl or ethyl.

[0067] R¹¹ preferably represents chloro or bromo.

[0068] k preferably represents 1.

[0069] As more preferred definitions in the formula (I) there can be mentioned:

[0070] R¹ more preferably represents chloro, bromo, methyl or methylsulfonyl,

[0071] R² more preferably represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl,

[0072] m more preferably represents 2, and in this case the two R¹ substituents are bond respectively to the 2-position and 4-position of a benzene ring and the two R¹ substituents may be identical or different.

[0073] n more preferably represents represents 1.

[0074] In a most preferred group of the inventive compounds the group

[0075] bonds to the 3-position (according to formula (I)) of the benzene ring.

[0076] In another most preferred group Q represents one of the following groups

[0077] The substituents among the different ranges of preference can be combined without limitation among each other.

[0078] limitation among each other.

[0079] However, as a preferred group of compounds there may be explicitly mentioned the compounds of the formula (I) wherein the substituents have the preferred meaning as described above, and as a more preferred group of compounds there may be explicitly mentioned the compounds of the formula (I) wherein the substituents have the more preferred meaning as described above.

[0080] The aforementioned preparation process (a) can be illustrated by the following reaction formula, in case of using, for example, 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate as the starting material.

[0081] The aforementioned preparation process (b) can be illustrated by the following reaction formula, in case of using, for example, 2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}cyclohexane-1,3-dione as the starting material, and, for example, oxalyl dichloride as chlorinating agent.

[0082] The aforementioned preparation process (c) can be illustrated by the following reaction formula, in case of using, for example, 3-chloro-2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one and thiophenol as the starting materials.

[0083] It is further mentioned that the group (Q-1) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms

[0084] It is also mentioned that the group (Q-2) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms

[0085] Thus, the compounds of the formula (I) of the present invention include the compounds of the formula (I) wherein Q represents the above-mentioned tautomeric groups (Q-1a), (Q-1b), (Q-2a) or (Q-2b) as group Q-1 or Q-2 respectively. In the present specification, however, it should be understood that these tautomeric groups are represented, unless specified, by the illustration of group (Q-1) or group (Q-2).

[0086] The compounds of the formula (II), the starting materials in the above-mentioned preparation process (a), are novel compounds which were not described in the literature up to the present and can be prepared according to the process described in various publications (e.g., Japanese Laid-open Patent Publications No. 222/1990, No. 173/1990, No. 6425/1990 etc.) by reacting compounds of the formula (IV)

[0087] wherein

[0088] R¹, R², m and n have the same definition as aforementioned, and

[0089] M represents halogen,

[0090] with compounds of the formula (V)

Q_(a-H)   (V)

[0091] wherein

[0092] Q_(a) represents one of the following groups

[0093] wherein

[0094] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as aforementioned,

[0095] in an appropriate diluent, for example, dichloromethane, in the presence of an appropriate condensing agent, for example, triethylamine.

[0096] The compounds of the formula (IV) used in the above-mentioned reaction are also novel compounds which were not described in the literature up to the present and can be prepared, for example, by reacting compounds of the formula (VI)

[0097] wherein

[0098] R¹, R², m and n have the same definition as aforementioned,

[0099] with a halogenating agent, for example, phosphorus oxychloride, phosphorus-oxy-bromide, phosphorus trichloride, phosphorus tribromide, phosgene, oxalyl dichloride, thionyl chloride, thionyl bromide.

[0100] The compounds of the formula (V) used as the starting materials in the preparation of the compounds of the above-mentioned formula (II) are per se known and commercially available or can be easily prepared according to the processes described in various publications (e.g., Japanese Laid-open Patent Publications No. 6425/1990, No. 265415/1998, No. 265441/1998).

[0101] The compounds of the formula (VI) used for the preparation of the compounds of the above-mentioned formula (IV) are also novel compounds which were not described in the literature up to the present and can be easily prepared, for example, by hydrolyzing compounds of the formula (VII)

[0102] wherein

[0103] R¹, R², m and n have the same definition as aforementioned, and

[0104] T² represents C₁₋₄ alkoxy, preferably methoxy or ethoxy,

[0105] in an appropriate diluent, for example, aqueous dioxane, in the presence of an appropriate base, for example, sodium hydroxide.

[0106] The compounds of the above-mentioned formula (VII) are also novel compounds and can be easily obtained, for example, by reacting compounds of the formula (VIII)

[0107] wherein

[0108] R² has the same definition as aforementioned

[0109] with compounds of the formula (IX)

[0110] wherein

[0111] R¹, m and n have the same definition as aforementioned,

[0112] T² represents C₁₋₄ alkyl, preferably methyl or ethyl, and

[0113] M represents halogen,

[0114] in an appropriate diluent, for example, N,N-dimethylformamide, in the presence of an appropriate condensing agent, for example, potassium carbonate.

[0115] The compounds of the above-mentioned formula (VIII) are known compounds described, for example, in Berichte Vol. 28, p. 74-76 (1895) and can be easily prepared according to the process described in said publication.

[0116] On the other hand, the compounds of the above-mentioned formula (IX), a part of which are novel compounds which were not described in the literature up to the present, can be easily prepared according to the process described, for example, in Japanese Laid-open Patent Publication No. 173/1990.

[0117] The compounds of the formula (II), the starting materials in the above-mentioned preparation process (a), can also be easily prepared from compounds of the aforementioned formula (VI) according to the process described, for example, in WO93/18031.

[0118] As typical examples of the compounds of the formula (II) used as the starting materials in the aforementioned preparation process (a), the followings can be mentioned:

[0119] 3-Oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0120] 3-oxo-1-cyclohexenyl 2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-fluorobenzoate,

[0121] 3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0122] 3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0123] 3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0124] 3-oxo-1-cyclohexenyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0125] 3-oxo-1-cyclohexenyl 4-bromo-2-{[(1-phenyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0126] 3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluorometh-ylbenzoate,

[0127] 3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylbenzoate,

[0128] 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0129] 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]meth-yl}benzoate,

[0130] 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-(2-chlorophenyl)-1H-tetrazol-5-yl)thio]-methyl}benzoate,

[0131] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-meth-ylsulfonylbenzoate,

[0132] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,

[0133] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-(n-pentyl)-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,

[0134] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-(3-difluoromethylphenyl)-1H-tetrazol-5-yl)-thio]methyl}-4-methylsulfonylbenzoate,

[0135] 3-oxo-1-cyclohexenyl 4-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-meth-ylsulfonylbenzoate,

[0136] 3-oxo-1-cyclohexenyl 2,4-dimethylsulfanyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoate,

[0137] 3-oxo-1-cyclohexenyl 4-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-meth-ylsulfonylbenzoate,

[0138] 3-oxo-1-cyclohexenyl 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0139] 3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-methoxybenzoate,

[0140] 3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-methylsulfonyloxybenzoate,

[0141] 3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate,

[0142] 3-oxo-1-cyclohexenyl 4-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate,

[0143] 5,5-dimethyl-3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoate,

[0144] 4,4-dimethyl-3-oxo-1-cyclohexenyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoate,

[0145] 4,4-dimethyl-3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)-thio]methyl}benzoate,

[0146] 4-{4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyloxy}-bicyclo[3.2.1]-3-octen-2-one,

[0147] 4-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyloxy}bi-cyclo[3.2.1]-3-octen-2-one,

[0148] 4-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyloxy}bicyclo[3.2.1]-3-octen-2-one.

[0149] As typical examples of the compounds of the formula (IV) used as the starting materials in the preparation of the compounds of the aforementioned formula (II), the followings can be mentioned:

[0150] 4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0151] 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0152] 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl chloride,

[0153] 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0154] 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0155] 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl chloride,

[0156] 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl chloride,

[0157] 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0158] 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0159] 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoyl chloride,

[0160] 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl bromide,

[0161] 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl bromide,

[0162] 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl bromide.

[0163] As typical examples of the compounds of the formula (VI) used as the starting materials in the preparation of the compounds of the aforementioned formula (IV), the followings can be mentioned:

[0164] 4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0165] 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0166] 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoic acid,

[0167] 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0168] 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0169] 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoic acid,

[0170] 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoic acid,

[0171] 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0172] 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thiolmethyl}benzoic acid,

[0173] 4-{[(1-methyl-1H-tetrazol-5-yl)thiolmethyl}-2-nitro-benzoic acid.

[0174] As typical examples of the compounds of the formula (VII) used as the starting materials in the preparation of the compounds of the aforementioned formula (VI), the followings can be mentioned.

[0175] Methyl 4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0176] methyl 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0177] methyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoate,

[0178] methyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0179] methyl 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0180] methyl 2chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}4-methylsulfonylbenzoate,

[0181] methyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate,

[0182] methyl 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0183] methyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0184] methyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoate,

[0185] ethyl 2,4-dichloro-3-{(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0186] ethyl 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-4-methylsulfonylbenzoate,

[0187] ethyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate.

[0188] The compounds of the formula (Ib), starting materials in the aforementioned preparation process (b), are a part of the compounds of the formula (I) of the present invention and can be easily prepared according to the above-mentioned preparation process (a).

[0189] As typical examples of the compounds of the formula (Ib) used as the starting materials in the aforementioned preparation process (b), the followings, included in the formula (I), can be mentioned:

[0190] 2-{4Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0191] 2-{4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0192] 2-{2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoyl}cyclo-hexane-1,3-dione,

[0193] 2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0194] 2-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}cyclo-hexane-1,3-dione,

[0195] 2-{2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl}-cyclohexane-1,3-dione,

[0196] 2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}cyclohexane-1,3-dione,

[0197] 2-{2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0198] 2-{2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0199] 2-{4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoyl}-cyclohexane-1,3-dione,

[0200] 3-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}bicyclo[3.2.1]-octane-2,4-dione

[0201] As a halogenating agent used for the reaction with the compounds of the formula (Ib) in the preparation process (b) there can be mentioned, for example, thionyl chloride, thionyl bromide, oxalyl dichloride, oxalyl dibromide etc.

[0202] The compounds of the formula (Ic), the starting materials in the aforementioned preparation process (c), are a part of the compounds of the formula (I) of the present invention and can be easily prepared according to the above-mentioned preparation process (b).

[0203] As typical examples of the compounds of the formula (Ic) used as the starting materials in the aforementioned preparation process (c), the followings, included in the formula (I), can be mentioned:

[0204] 3-Chloro-2-{4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0205] 3-chloro-2-{4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0206] 3-chloro-2-{2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl}-2-cyclohexen-1-one,

[0207] 3-chloro-2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0208] 3-chloro-2-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one,

[0209] 3-chloro-2-{2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}-2-cyclohexen-1-one,

[0210] 3 -chloro-2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl}-2-cyclohexen-1-one,

[0211] 3-chloro-2-{2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclo-hexen-1-one,

[0212] 3-chloro-2-{2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0213] 3-chloro-2-{4-{[(1-methyl-1H-tetrazol-5 -yl)thio]methyl}-2-nitrobenzoyl}-2-cyclohexen-1-one,

[0214] 4-chloro-2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methyl-sulfonylbenzoyl}bicyclo[3.2.1]-3-octen-2-one.

[0215] The compounds of the formula (III), the starting materials in the above-mentioned preparation process (c), are thiol compounds well known in the field of organic chemistry and as typical examples of the compounds of the formula (III) the followings can be mentioned:

[0216] Methyl mercaptan,

[0217] ethyl mercaptan,

[0218] thiophenol,

[0219] 4-fluorothiophenol,

[0220] 4-chlorothiophenol,

[0221] 2-methylthiophenol,

[0222] 4-ethylthiophenol,

[0223] 4-trifluoromethylthiophenol etc.

[0224] Each compound of the formulae (II), (IV), (VI) and (VII), starting material or intermediate product in the aforementioned processes (a)-(c) for the preparation of the compounds of the formula (I) of the present invention is a novel compound which was not described in the literature up to the present. The compounds can be illustrated collectively by the following general formula (X)

[0225] wherein

[0226] W represents T¹, hydroxy or T², wherein

[0227] R¹, R², m, n, T¹, T² and M have the same definition as aforementioned.

[0228] The reaction of the aforementioned preparation process (a) can be conducted in an appropriate diluent. As examples of such diluents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, toluene, dichloromethane, chloroform and 1,2-dichloroethane; ethers, for example, ethyl ether, dimethoxyethane (DME) and tetrahydrofuran (THF); ketones, for example, methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile; esters, for example, ethyl acetate; acid amides, for example, dimethylformamide (DMF).

[0229] The preparation process (a) can be conducted in the presence of a cyanide and a base. As a cyanide usable in that case there can be mentioned, for example, sodium cyanide, potassium cyanide, acetone cyanohydrin and hydrogen cyanide. As a base there can be mentioned, for example, as inorganic bases, hydroxides and carbonates of alkali metals and alkaline earth metals, for example, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

[0230] The aforementioned preparation process (a) can be conducted also in the co-existence of a phase-transfer catalyst. As examples of the phase-transfer catalyst usable in that case there can be mentioned crown ethers, for example, dibenzo-18-crown-6, 18-crown-6 and 15-crown-5.

[0231] The reaction of the preparation process (a) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about −10 to about 80° C., preferably about 5 to about 40° C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

[0232] In conducting the preparation process (a) the target compounds of the afore-mentioned formula (I), in case that Q represents groups (Q-1) or (Q-2), can be obtained, for example, by reacting 1 mole of a compound of the formula (II) with 1 to 4 moles of triethylamine in a diluent, for example, acetonitrile, in the presence of 0.01 to 0.5 moles of acetone cyanohydrin.

[0233] In conducting the preparation process (a) it is possible to obtain the compounds of the formula (I) by conducting reactions starting from the compounds of the aforementioned formula (VI) continuously in one pot without isolating the compounds of the formulae (I) and (II).

[0234] The reaction of the aforementioned preparation process (b) can be conducted in an appropriate diluent. As examples of such there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chloro-benzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile and propionitrile; esters, for example, ethyl acetate and amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and hexamethyl-phosphoric triamide (HMPA).

[0235] The reaction of the preparation process (b) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about −20 to about 100° C., preferably about 0 to about 50° C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

[0236] In conducting the preparation process (b) the target compounds of the afore-mentioned formula (I), in case that Q represents groups (Q-6) or (Q-7), wherein R¹¹ in said group represents chloro or bromo, can be obtained, for example, by reacting 1 mole of a compound of the formula (Ib) with 1 to 5 moles of oxalyl dichloride in a diluent, for example, dichloromethane.

[0237] The reaction of the aforementioned preparation process (c) can be conducted in an appropriate diluent. As examples of such diluents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile and acrylonitrile; esters, for example, ethyl acetate and amyl acetate; acid amides, for example, dimethyl-formamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone; sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) and sulfolane; bases, for example, pyridine.

[0238] The preparation process (c) can be conducted in the presence of a condensing agent. As a usable condensing agent there can be for example mentioned, as inorganic bases, hydrides and carbonates of alkali metals, for example, sodium hydride, lithium hydride, sodium carbonate and potassium carbonate; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), pyridine, 4-dimethylaminopyridine (MAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

[0239] The reaction of the preparation process (c) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about −20 to about 140° C., preferably about 0 to about 100° C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

[0240] In conducting the preparation process (c) the target compounds of the afore-mentioned formula (I), in case that Q represents groups (Q-3), (Q-4) or (Q-5) can be obtained, for example, by reacting 1 mole of a compound of the formula (Ic) with 1 to 5 moles of thiophenol in a diluent, for example, tetrahydrofuran in the presence of 1 to 5 moles of triethylamine.

[0241] The active compounds of the aforementioned formula (I), according to the present invention, show, as shown in the biological test examples to be described later, excellent herbicidal activities against various weeds and can be used as herbicides. In the present specification weeds mean, in the broadest sense, all plants which grow in locations where they are undesired. The compounds, according to the present invention, act as total or selective herbicides depending upon the applied concentration. The active compounds, according to the present invention, can be used, for example, between the following weeds and cultures.

[0242] Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Cheno-podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia etc.

[0243] Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.

[0244] Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon etc.

[0245] Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc.

[0246] The use of the compounds, according to the present invention, is not restricted to the above-mentioned plants, but may be applied to other plants in the same manner. The active compounds, according to the present invention, can, depending upon the applied concentration, non-selectively control weeds and can be used, for example, on industrial terrain, rail tracks, paths, places with or without tree plantings. Moreover, the active compounds, according to the present invention, can be used for controlling weeds in perennial cultures and applied in, for example, afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hopfields etc. and can be applied also for the selective controlling of weeds in annual cultures.

[0247] According to the invention all plants and plant parts can be treated. The term plants includes all plants and plant populations, such as desired or undesired wild plants and cultivated plants (including naturally occurring cultivated varieties). Cultivated plants can be plant varieties that were obtained by conventional breeding and optimizing processes or by biotechnological and genetic engineering methods or a combination of such processes and methods, including transgenic plants and including plant varieties that cannot or can be protected by plant patents or plant variety rights. Plant parts are all parts and organs of plants occurring above or below the surface of the soil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers, fruits and seeds as well as roots, tubers, bulbs and rhizomes. The term plant parts also includes harvested crops and propagation material, e.g. cuttings, tubers, bulbs, rhizomes, shoots and seeds.

[0248] According to the invention the plants and plant parts are treated using the usual methods by applying the active ingredients or compositions containing them directly to the plants or plant parts or to their surroundings (including the soil) or storeroom, e.g. by dipping, spraying, dusting, fogging, spreading and in the case of propagation material also by coating using one or multiple layers.

[0249] The active compounds, according to the present invention, can be made into the customary formulations. As such formulations there can be mentioned, for example, solutions, wettable powders, emulsions, suspensions, powders, water-dispersible granules, tablets, granules, suspension-emulsion concentrates, microcapsules in polymeric substances, jumbo formulations etc.

[0250] These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.

[0251] As liquid diluents or carriers there can be mentioned, for example, aromatic hydro-carbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycol etc.) and their ethers, esters etc., ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulphoxide etc.) and water. In case of using water as extender, for example, organic solvents can be used as auxiliary solvents.

[0252] As solid diluents or carriers there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc. As solid carriers for granules there can be mentioned, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc.), synthetic granules of inorganic and organic meals, particles of organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks etc.) etc.

[0253] As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates etc.)], albumin hydrolysis products etc.

[0254] Dispersants include, for example, ligninsulphite waste liquor, methyl cellulose etc.

[0255] Tackifiers can also be used in formulations (powders, granules, emulsions). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate etc.).

[0256] Colorants can also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc.) and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc.

[0257] Said formulations can contain the active compounds of the formula (I) in a range of generally 0.1 to 95% by weight, preferably 0.5 to 90% by weight.

[0258] The active compounds of the formula (I), according to the present invention, can be used as such or in their formulation forms for controlling weeds. They can be used also as a mixed agent with known herbicides. Such a mixed agent can be previously prepared as a final formulation form or can be prepared by tank-mixing on occasion of application. As herbicides usable in combination with the compounds of the formula (I), according to the present invention, as a mixed agent there can be specifically mentioned, for example, the following herbicides shown in common names.

[0259] Acetamide type herbicides, for example, pretilachlor, butachlor, tenylchlor, alachlor etc.;

[0260] amide type herbicides, for example, clomeprop, etobenzanid etc.;

[0261] benzofuran type herbicides, for example, benfuresate etc.;

[0262] indanedione type herbicides, for example, indanofan etc.;

[0263] pyrazole type herbicides, for example, pyrazolate, benzofenap, pyrazoxyfen etc.;

[0264] oxazinone type herbicides, for example, oxaziclomefone etc.;

[0265] sulfonylurea type herbicides, for example, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamron Ethoxysulfuron, Halosulfuron (-methyl) etc.;

[0266] thiocarbamate type herbicides, for example, thiobencarb, molinate, pyributycarb etc.;

[0267] triazine type herbicides, for example, dimethametryn Simetryn etc.;

[0268] triazole type herbicides, for example, cafenstrole etc.;

[0269] quinoline type herbicides, for example, quinclorac etc.;

[0270] isoxazole type herbicides, for example, isoxaflutole etc.;

[0271] dithiophosphate type herbicides, for example, anilofos etc.;

[0272] oxyacetamide type herbicides, for example, mefenacet, flufenacet etc.;

[0273] tetrazolinone type herbicides, for example, fentrazamide etc.;

[0274] dicarboxyimide type herbicides, for example, pentoxazone etc.;

[0275] trione type herbicides, for example, sulcotrione, benzobicyclon etc.;

[0276] phenoxypropinate type herbicides, for example, cyhalofop-butyl etc.;

[0277] benzoic acid type herbicides, for example, pyriminobac-methyl etc.;

[0278] diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.;

[0279] pyridinedicarbothioate type herbicides, for example, dithiopyr etc.;

[0280] phenoxy type herbicides, for example, MCPA, MCPB etc.;

[0281] urea type herbicides, for example, dymron, cumyluron etc.;

[0282] naphthalenedione type herbicides, for example, quinoclamine etc.;

[0283] isoxazolidinone type herbicides, for example, clomazone etc.

[0284] diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.;

[0285] pyridinedicarbothioate type herbicides, for example, dithiopyr etc.;

[0286] phenoxy type herbicides, for example, MCPA, MCPB etc.;

[0287] urea type herbicides, for example, dymron, cumyluron etc.;

[0288] naphthalenedione type herbicides, for example, quinoclamine etc.;

[0289] isoxazolidinone type herbicides, for example, clomazone etc.

[0290] In addition to the above mentioned herbicides, the following herbicides, shown in common names, for example, Acetochlor, Acifluorfen (-sodium), Aclonifen, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Amitrole, Asulam, Atrazine, Azafenidin, Beflubutamid, Benazolin (-ethyl), Bentazon, Benzfendizone, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac-(sodium), Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butafenacil-(allyl), Butenachlor, Butralin, Butroxydim, Butylate, Carbetamide, Carfentrazone (-ethyl), Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulf-uron, Chlorthiamid, Chlortoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Clefoxydim, Clethodim, Clodinafop (-propargyl), Clopyralid, Cloransulam (-methyl), Cyanazine, Cybutryne, Cycloate, Cycloxydim, 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichlobenil, Dichlorprop (-P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenopenten (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dikegulac (-sodium), Dimefuron, Dimepiperate, Dimethachlor, Dimethenamid (-P), Dimexyflam, Dinitramine, Diphenamid, Diquat (-dibromide), Diuron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethiozin, Ethofumesate, Ethoxyfen, Fenoxaprop (-P-ethyl), Flamprop (-M-isopropyl, -M-methyl), Flazasulfuron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Fluchloralin, Flumetsulam, Flumiclorac (-pentyl), Flumiox-azin, Flumipropyn, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxypropyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fomesafen, Foramsulfuron, Glufosinate (-ammonium), Glyphosate (-ammonium, -isopropylammonium), Halosafen, Haloxyfop (-ethoxy-ethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imaza-mox, Imazapic, Imazapyr, Inazaquin, Imazethapyr, Iodosulfuron (-methyl, -sodium), Ioxynil, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxadifen (-ethyl), Isoxapyrifop, Ketospiradox, Lactofen, Lenacil, Linuron, Mecoprop (-P), Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Methyldymron, Metobenzuron, Metobromuron, (S-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Paraquat, Pelargonsäure, Pendimethalin, Pendralin, Pethoxamid, Phenmedioham, Picolinafen, Piperophos, Primisulfuron (-methyl), Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazogyl, Pyribenzoxim, Pyridafol, Pyridate, Pyridatol, Pyriftalid, Pyrithiobac (-sodium), Quinmerac, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Tiocarbazil, Tralkoxydim, Triallate, Triasulfiuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifloxy-sulfuron, Trifluralin, Triflusulfuron (-methyl), Tritosulfuron.

[0291] The above-mentioned herbicides are known herbicides mentioned in “Pesticide Manual” 2000, published by The British Crop Protect Council.

[0292] The weight ratios of the groups of active substances in the mixed compositions can vary within relatively wide ranges.

[0293] For instance, per part by weight of (1) the compounds of the formula (I),

[0294] 0.2 to 14 parts by weight of acetamide type herbicides,

[0295] preferably 0.66 to 5 parts by weight;

[0296] 2 to 40 parts by weight of amide type herbicides,

[0297] preferably 3.96 to 16 parts by weight;

[0298] 0.2 to 20 parts by weight of benzofuran type herbicides,

[0299] preferably 1.00 to 6 parts by weight;

[0300] 0.2 to 8 parts by weight of indanedione type herbicides,

[0301] preferably 0.49 to 2 parts by weight;

[0302] 0.06 to 4 parts by weight of oxazinone type herbicides,

[0303] preferably 0.20 to 0.8 parts by weight;

[0304] 0.02 to 4 parts by weight of sulfonylurea type herbicides,

[0305] preferably 0.07 to 1.2 parts by weight;

[0306] 1 to 100 parts by weight of thiocarbamate type herbicides,

[0307] preferably 2.47 to 40 parts by weight;

[0308] 0.6 to 12 parts by weight of triazine type herbicides,

[0309] preferably 1.32 to 4.5 parts by weight;

[0310] 0.1 to 8 parts by weight of triazole type herbicides,

[0311] preferably 0.33 to 3 parts by weight;

[0312] 0.2 to 10 parts by weight of dithiophosphate type herbicides,

[0313] preferably 1.00 to 4 parts by weight;

[0314] 0.2 to 50 parts by weight of oxyacetamide type herbicides,

[0315] preferably 1.00 to 12 parts by weight;

[0316] 0.02 to 10 parts by weight of tetrazolinone type herbicides,

[0317] preferably 0.17 to 3 parts by weight;

[0318] 0.1 to 12 parts by weight of dicarboxyimide type herbicides,

[0319] preferably 0.33 to 4.5 parts by weight;

[0320] 0.2 to 12 parts by weight of phenoxypropinate type herbicides,

[0321] preferably 0.4 to 1.8 parts by weight;

[0322] 0.6 to 20 parts by weight of diphenylether type herbicides,

[0323] preferably 1.65 to 7.5 parts by weight;

[0324] 0.02 to 14 parts by weight of pyridinedicarbothioate type herbicides,

[0325] preferably 0.20 to 5 parts by weight;

[0326] 0.2 to 10 parts by weight of phenoxy type herbicides,

[0327] preferably 0.66 to 4parts by weight,

[0328] and

[0329] 2 to 80 parts by weight of urea type herbicides,

[0330] preferably 4.95 to 25 parts by weight,

[0331] are used.

[0332] Furthermore, the active compounds of the formula (I), according to the present invention, can be mixed also with a safener and their application as a selective herbicide can be broadened to reduce phytotoxicity and to provide wider weed-control-spectrum by such a mixing.

[0333] As an example of the safener, the following safeners can be mentioned;

[0334] AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flurazole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), MCPA, Mecoprop (-P), Mefenpyr (-diethyl), MG-191, Naphthalic anhydride, Oxabetrinil, PPG-1292, R-29148.

[0335] The above-mentioned safeners are known safeners mentioned in “Pesticide Manual”, 2000, published by The British Crop Protect Council.

[0336] The weight ratios of the groups of active substances in the mixed comositions can vary within relatively wide ranges.

[0337] For instance, per part by weight of (1) the compounds of the formula (I),

[0338] 0.05 to 50 parts by weight of Dichlormid,

[0339] preferably 0.1 to 1 0 parts by weight;

[0340] 0.05 to 50 parts by weight of Dymron,

[0341] preferably 0.1 to 10 parts by weight;

[0342] 0.05 to 50 parts by weight of Fenclorim,

[0343] preferably 0.1 to 10 parts by weight;

[0344] 0.05 to 50 parts by weight of Mefenpyr (-diethyl),

[0345] preferably 0.1 to 10 parts by weight;

[0346] and

[0347] 0.05 to 50 parts by weight of Naphthalic anhydride,

[0348] preferably 0.1 to 10 parts by weight,

[0349] are used.

[0350] And furthermore, the above-mentioned combinations of the compounds of the formula (I), according to the present invention, and the above-mentioned herbicides can be mixed with also the above-mentioned safeners and their application as selective herbicidal compositions can be broadened to reduce phytotoxicity and to provide wider weed—control spectrum by mixing safeners and/or other selective herbicides.

[0351] Surprisingly, some of the mixed compositions, according to the present invention show synergistic effects.

[0352] In case of using the active compounds of the formula (I) and their mixed compositions, according to the present invention, they can be directly used as such or used in formulation forms such as ready-to-use solutions, emulsions, tablets, suspensions, powders, pastes, granules or used in the use forms prepared by further dilution. The active compounds of the present invention can be applied by means of, for example, watering, spraying, atomizing, granule application etc.

[0353] The active compounds of the formula (I) and their mixed compositions, according to the present invention, can be used at any stages before and after germination of plants. They can also be taken into the soil before sowing.

[0354] The application amount of the active compounds of the formula (I) and their mixed compositions, according to the present invention, can be varied in a substantial range and are fundamentally different according to the nature of the desired effect. In case of using as herbicides, as the application amount there can be mentioned, for example, ranges of about 0.01 to about 3 kg, preferably about 0.05 to about 1 kg of the active compounds per hectare.

[0355] The preparations and applications of the compounds and their mixed compositions according to the present invention, will be described more specifically by the following examples. However, the present invention should not be restricted to them in any way.

Synthesis Example 1

[0356]

[0357] 3-Oxo-1-cyclohexenyl 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-meth-ylsulfonylbenzoate (0.83 g) was dissolved in acetonitrile (20 ml), to which triethylamine (0.34 g) and acetone cyanohydrin (10 mg) were added and the mixture was stirred at room temperature for 5 hours. After distilling off the solvent, the mixture was acidified by addition of diluted hydrochloric acid and extracted with dichloromethane (150 ml). The organic layer was washed with a saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. Dichloromethane was distilled off to obtain the objected 2-{2-chloro-3-{[(1-ethyl-1H-tetrazol-1-yl)thio]methyl}-4-methylsulfonylbenzoyl}cyclohexane-1,3-dione (0.75 g). mp: 67-71° C.

Synthesis Example 2

[0358]

[0359] To a solution of 2-{2-chloro-4-methylsulfonyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoyl}cyclohexane-1,3-dione (1.0 g) in dichloromethane (100 ml), oxalyl chloride (0.91 g) and 2 drops of N,N-dimethylformamide were added dropwise and the mixture was refluxed for 3 hours. The residue obtained by distilling off the solvent after the reaction was purified by silica gel column chromatography (eluant:ethyl acetate:hexane=7:3) to obtain the objective 3-chloro-2-{2-chloro4-methylsulfonyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one (0.71 g). IR (NaCl):=1662, 1310, 1279, 1150 cm⁻¹.

Synthesis Example 3

[0360]

[0361] 3-Chloro-2-{2-chloro-4-methylsulfonyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]meth-yl}benzoyl}-2-cyclohexen-1-one (0.75 g) and thiophenol (0.19 g) were dissolved in tetrahydrofuran (7 ml), to which a solution of triethylamine (0.19 g) in tetrahydro-furan (3 ml) was added dropwise at 5° C. and the mixture was stirred at room temperature for 4 hours. After the reaction cold water was added to the mixture, extracted with ethyl acetate (50 ml) and dried with anhydrous magnesium sulfate.

[0362] The residue obtained by distilling off the ethyl acetate was purified by silica gel column chromatography (eluant:ethyl acetate:hexane=7:3) to obtain the objective 2-{2-chloro-4-methylsulfonyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]meth-yl}benzoyl}-3-phenylthio-2-cyclohexen-1-one (0.61 g). mp: 76-87° C.

[0363] The compounds, obtained in the same manner as the above-mentioned Synthesis Examples 1-3, are shown in the following Tables 1-3, together with the compounds synthesized in the Synthesis Examples 1-3.

[0364] Examples of the compounds in case the compound of the formula (I) of the present invention is represented by the formula

[0365] are shown in Table 1,

[0366] examples of the compounds in case they are represented by the following formula

[0367] are shown in Table 2, and

[0368] examples of the compounds in case they are represented by the following formula

[0369] are shown in Table 3.

[0370] In Tables 1, 2 and 3,

[0371] Q1a a represents the group

[0372] Q1b represents the group

[0373] Q1c represents the group

[0374] Q2 represents the group

[0375] Q3a a represents the group

[0376] Q3b represents the group

[0377] Q3c represents the group

[0378] Q3d represents the group

[0379] Q3e represents the group

[0380] Q3f represents the group

[0381] Q3g represents the group

[0382] Q3h represents the group

[0383] Q3i represents the group

[0384] Q3j represents the group

[0385] Q3k represents the group

[0386] Q3l represents the group

[0387] Q3m represents the group

[0388] Q3n represents the group

[0389] Q3o represents the group

[0390] Q3p represents the group

[0391] Q3q represents the group

[0392] Q3r represents the group

[0393] Q3s represents the group

[0394] Q3t represents the group

[0395] Q3u represents the group

[0396] Q3v represents the group

[0397] Q3w represents the group

[0398] Q3x represents the group

[0399] Q3y represents the group

[0400] Q3z represents the group

[0401] Q3za represents the group

[0402] Q3zb represents the group

[0403] Q3zc represents the group

[0404] Q3zd represents the group

[0405] Q4a represents the group

[0406] Q4b represents the group

[0407] Q4c represents the group

[0408] Q4d represents the group

[0409] Q5a represents the group

[0410] Q5b represents the group

[0411] Q5c represents the group

[0412] Q5d represents the group

[0413] Q5e represents the group

[0414] Q5f represents the group

[0415] Q6a represents the group

[0416] Q6b represents the group

[0417] Q7 represents the group

[0418] Me represents methyl, Et represents ethyl, n-Pr represents n-propyl, i-Pr represents isopropyl, n-Bu represents n-butyl, t-Bu represents tert-butyl,n-Hex represents n-hexyl, OMe represents methoxy, OEt represents ethoxy, SMe represents methylthio, SEt represents ethylthio, SO₂Me represents methylsulfonyl, SO₂Et represents ethylsulfonyl, SO₂n-Pr represents n-propylsulfonyl, OSO₂Me represents methyl-sulfonyloxy, OSO₂Et represents ethylsulfonyloxy and Ph represents phenyl. TABLE 1

Com- pound melting point No. Y Z R n Q (mp) or n_(D) ²⁰ I-1  H H Me 1 Q1a I-2  H H Me 2 Q1a I-3  H H Me 1 Q2 I-4  OMe H Me 1 Q1a I-5  Cl H Me 1 Q1a I-6  Me H Me 1 Q1a I-7  H F Me 1 Q1a I-8  H F Me 1 Q2 I-9  H F Me 1 Q3a I-10 H F Me 1 Q5a I-11 H F Me 1 Q6a I-12 H F Et 1 Q1a I-13 H F

Q1a I-14 H Cl Me 1 Q1a I-15 H Cl Me 2 Q1a I-16 H Cl Me 1 Q2 I-17 H Cl Me 1 Q3a I-18 H Cl Me 1 Q5a I-19 H Cl Me 1 Q7 I-20 H Cl Et 1 Q1a I-21 H Cl

1 Q1a I-22 H Br Me 1 Q1a 1.6212 I-23 H Br Me 1 Q2 I-24 H Br Me 1 Q3a I-25 H Br Me 1 Q5a I-26 H Br Me 1 Q6a I-27 H Br Et 1 Q1a I-28 H Br

1 Q1a I-29 H I Me 1 Q1a I-30 H I Me 1 Q2 I-31 H I Me 1 Q3a I-32 H I Me 1 Q5a I-33 H I Et 1 Q1a I-34 H I

1 Q1a I-35 H Me Me 1 Q1a I-36 H CF₃ Me 1 Q1a I-37 H CF₃ Me 1 Q2 I-38 H CF₃ Me 1 Q3a I-39 H CF₃ Me 1 Q5a I-40 H CF₃ Me 1 Q6a I-41 H CF₃ Me 1 Q7 I-42 H CF₃ Et 1 Q1a I-43 H CF₃

1 Q1a I-44 H OMe Me 1 Q1a I-45 H OMe Me 1 Q2 I-46 H OMe Me 1 Q3a I-47 H OMe Me 1 Q5a I-48 H OMe Me 1 Q6a I-49 H OMe Et 1 Q1a I-50 H OMe

1 Q1a I-51 H OSO₂Me Me 1 Q1a I-52 H OSO₂Me Me 1 Q2 I-53 H SMe Me 1 Q1a I-54 H SMe Me 1 Q2 I-55 H SO₂Me Me 1 Q1a I-56 H SO₂Me Me 1 Q2 I-57 H SO₂Me Me 1 Q3a I-58 H SO₂Me Me 1 Q5 I-59 H SO₂Me Me 1 Q6a I-60 H SO₂Me Et 1 Q1a I-61 H SO₂Me

1 Q1a I-62 H NO₂ Me 1 Q1a I-63 H NO₂ Me 1 Q2 I-64 H NO₂ Me 1 Q3a I-65 H NO₂ Me 1 Q5a I-66 H NO₂ Et 1 Q1a I-67 H NO₂

1 Q1a I-68 H CN Me 1 Q1a I-69 H CN Me 1 Q2 I-70 H CN Me 1 Q3a I-71 H CN Me 1 Q5a I-72 H CN Et 1 Q1a I-73 H CN

1 Q1a I-74 H OCHF₂ Me 1 Q1a I-75 H OCHF₂ Me 1 Q2 I-76 H OCHF₂ Me 1 Q3a I-77 H OCHF₂ Me 1 Q5a I-78 H OCHF₂ Me 1 Q6a I-79 H OCHF₂ Et 1 Q1a I-80 H OCHF₂

1 Q1a I-81 H OCF₃ Me 1 Q1a I-82 H OCF₃ Me 1 Q2 I-83 H OCF₃ Me 1 Q3a I-84 H OCF₃ Me 1 Q5a I-85 H OCF₃ Et 1 Q1a I-86 H OCF₃

1 Q1a

[0419] TABLE 2

Compound No. X Z R n Q melting point (mp) or n_(D) ²⁰ II-1  H H Me 1 Q1a II-2  H H Me 2 Q1a II-3  H H Me 1 Q2 II-4  OMe H Me 1 Q1a II-5  OMe H Me 1 Q2 II-6  OSO₂Me H Me 1 Q1a II-7  OSO₂Me H Me 1 Q2 II-8  NO₂ H Me 1 Q1a II-9  NO₂ H Me 1 Q2 II-10  F Cl Me 1 Q1a 66-72 II-11  F Cl Me 1 Q2 II-12  F Cl Me 1 Q3a II-13  F Cl Me 1 Q5a II-14  F Cl

1 Q1a II-15  F Cl

1 Q2 II-16  F Cl

1 Q3a II-17  F Cl

1 Q5a II-18  Cl Cl Me 1 Q1a 1.6010 II-19  Cl Cl Me 2 Q1a II-20  Cl Cl Me 1 Q1b II-21  Cl Cl Me 1 Q1c II-22  Cl Cl Me 1 Q2 II-23  Cl Cl Me 1 Q3a II-24  Cl Cl Me 1 Q3b II-25  Cl Cl Me 1 Q3d II-26  Cl Cl Me 1 Q4a II-27  Cl Cl Me 1 Q4b II-28  Cl Cl Me 1 Q5a II-29  Cl Cl Me 1 Q5c II-30  Cl Cl Me 1 Q6a II-31  Cl Cl Me 1 Q7 II-32  Cl Cl Et 1 Q1a II-33  Cl Cl Et 2 Q1a II-34  Cl Cl Et 1 Q1b II-35  Cl Cl Et 1 Q1c II-36  Cl Cl Et 1 Q2 II-37  Cl Cl Et 1 Q3a II-38  Cl Cl Et 1 Q3f II-39  Cl Cl Et 1 Q4a II-40  Cl Cl Et 1 Q4b II-41  Cl Cl Et 1 Q5a II-42  Cl Cl Et 1 Q5d II-43  Cl Cl Et 1 Q6a II-44  Cl Cl Et 1 Q7 II-45  Cl Cl n-Pr 1 Q1a II-46  Cl Cl n-Pr 1 Q2 II-47  Cl Cl n-Pr 1 Q3a II-48  Cl Cl n-Pr 1 Q5a II-49  Cl Cl i-Pr 1 Q1a II-50  Cl Cl i-Pr 1 Q2 II-51  Cl Cl i-Pr 1 Q3a II-52  Cl Cl i-Pr 1 Q5a II-53  Cl Cl

1 Q1a II-54  Cl Cl

1 Q1b II-55  Cl Cl

1 Q1c II-56  Cl Cl

1 Q2 II-57  Cl Cl

1 Q3a II-58  Cl Cl

1 Q3e II-59  Cl Cl

1 Q4a II-60  Cl Cl

1 Q4b II-61  Cl Cl

1 Q5a II-62  Cl Cl

1 Q6a II-63  Cl Cl

1 Q7 II-64  Cl Cl

1 Q1a II-65  Cl Cl

1 Q1a II-66  Cl Cl

1 Q1a II-67  Cl Cl

1 Q2 II-68  Cl Cl —CH═CH₂ 1 Q1a II-69  Cl Cl —CH═CH₂ 1 Q1b II-70  Cl Cl —CH═CH₂ 1 Q1c II-71  Cl Cl —CH═CH₂ 1 Q2 II-72  Cl Cl —CH═CH₂ 1 Q3a II-73  Cl Cl —CH═CH₂ 1 Q4a II-74  Cl Cl —CH═CH₂ 1 Q4b II-75  Cl Cl —CH═CH₂ 1 Q5a II-76  Cl Cl —CH═CH₂ 1 Q6a II-77  Cl Cl —CH₂CH═CH₂ 1 Q1a II-78  Cl Cl —CH₂CH═CH₂ 1 Q2 II-79  Cl Cl —CH₂CH═CH₂ 1 Q3a II-80  Cl Cl —CH₂CH═CH₂ 1 Q5a II-81  Cl Cl Ph 1 Q1a II-82  Cl Cl 2-Cl-Ph 1 Q1a II-83  Cl Cl 2-Me-Ph 1 Q1a II-84  Cl Cl 3-CF₃-Ph 1 Q1a II-85  Cl Cl CH₂CH₂F 1 Q1a II-86  Cl Cl CH₂CH₂F 1 II-87  Cl Cl CH₂CH₂F 1 Q3a II-88  Cl Cl CH₂CH₂F 1 Q5a II-89  Cl Cl CH₂CH₂F 1 Q6a II-90  Cl Cl CH₂CH₂Cl 1 Q1a II-91  Cl Cl CH₂CH₂Cl 1 Q2 II-92  Cl Cl CH₂CH₂Cl 1 Q3a II-93  Cl Cl CH₂CH₂Cl 1 Q5a II-94  Cl Cl CH₂CF₃ 1 Q1a II-95  Cl Cl CH₂CF₃ 1 Q1b II-96  Cl Cl CH₂CF₃ 1 Q1c II-97  Cl Cl CH₂CF₃ 1 Q2 II-98  Cl Cl CH₂CF₃ 1 Q3a II-99  Cl Cl CH₂CF₃ 1 Q4a II-100 Cl Cl CH₂CF₃ 1 Q4b II-101 Cl Cl CH₂CF₃ 1 Q5a II-102 Cl Cl CH₂CF₃ 1 Q6a II-103 Cl Cl CH₂CF₃ 1 Q7 II-104 Cl Cl CH₂CF₂CF₃ 1 Q1a II-105 Cl Cl CH₂CF₂CF₃ 1 Q2 II-106 Cl Cl CH₂CF₂CF₃ 1 Q3a II-107 Cl Cl CH₂CH₂CH₂F 1 Q5a II-108 Cl Cl CH₂CH₂CH₂F 1 Q1a II-109 Cl Cl CH₂CH₂CH₂F 1 Q2 II-110 Cl Cl CH₂CH₂CH₂F 1 Q3a II-111 Cl Cl CH₂CH₂CH₂F 1 Q5a II-112 Cl SMe Me 1 Q1a II-113 Cl SMe Me 1 Q2 II-114 Cl SMe Et 1 Q1a II-115 Cl SMe

1 Q1a II-116 Cl SMe —CH═CH₂ 1 Q1a II-117 Cl SO₂Me Me 1 Q1a 78-84 II-118 Cl SO₂Me Me 1 Q1a II-119 Cl SO₂Me Me 1 Q1b II-120 Cl SO₂Me Me 1 Q1c II-121 Cl SO₂Me Me 1 Q2 60-63 II-122 Cl SO₂Me Me 1 Q3a 76-87 II-123 Cl SO₂Me Me 1 Q3c 210-211 II-124 Cl SO₂Me Me 1 Q3 II-125 Cl SO₂Me Me 1 Q4a 79-82 II-126 Cl SO₂Me Me 1 Q4b II-127 Cl SO₂Me Me 1 Q5a II-128 Cl SO₂Me Me 1 Q5f II-129 Cl SO₂Me Me 1 Q6a II-130 Cl SO₂Me Me 1 Q7 II-131 Cl SO₂Me Et 1 Q1a 67-71 II-132 Cl SO₂Me Et 2 Q1a II-133 Cl SO₂Me Et 1 Q1b II-134 Cl SO₂Me Et 1 Q1c II-135 Cl SO₂Me Et 1 Q2 II-136 Cl SO₂Me Et 1 Q3a II-137 Cl SO₂Me Et 1 Q3b II-138 Cl SO₂Me Et 1 Q4a II-139 Cl SO₂Me Et 1 Q4b II-140 Cl SO₂Me Et 1 Q5a II-141 Cl SO₂Me Et 1 Q5b II-142 Cl SO₂Me Et 1 Q6a II-143 Cl SO₂Me Et 1 Q7 II-144 Cl SO₂Me n-Pr 1 Q1a 142-145 II-145 Cl SO₂Me n-Pr 1 Q2 II-146 Cl SO₂Me n-Pr 1 Q3a II-147 Cl SO₂Me n-Pr 1 Q5a II-148 Cl SO₂Me i-Pr 1 Q1a 69-73 II-149 Cl SO₂Me i-Pr 1 Q2 II-150 Cl SO₂Me i-Pr 1 Q3a II-151 Cl SO₂Me i-Pr 1 Q5a II-152 Cl SO₂Me

1 Q1a 79-84 II-153 Cl SO₂Me

1 Q1b II-154 Cl SO₂Me

1 Q1c II-155 Cl SO₂Me

1 Q2 II-156 Cl SO₂Me

1 Q3a II-157 Cl SO₂Me

1 Q3d II-158 Cl SO₂Me

1 Q4a II-159 Cl SO₂Me

1 Q4b II-160 Cl SO₂Me

1 Q5a II-161 Cl SO₂Me

1 Q6a II-162 Cl SO₂Me

1 Q7 II-163 Cl SO₂Me

1 Q1a II-164 Cl SO₂Me

1 Q2 II-165 Cl SO₂Me

1 Q1a II-166 Cl SO₂Me

1 Q1a II-167 Cl SO₂Me

1 Q2 II-168 Cl SO₂Me —CH═CH₂ 1 Q1a II-169 Cl SO₂Me —CH═CH₂ 1 Q1b II-170 Cl SO₂Me —CH═CH₂ 1 Q1c II-171 Cl SO₂Me —CH═CH₂ 1 Q2 II-172 Cl SO₂Me —CH═CH₂ 1 Q3a II-173 Cl SO₂Me —CH═CH₂ 1 Q4a II-174 Cl SO₂Me —CH═CH₂ 1 Q4b II-175 Cl SO₂Me —CH═CH₂ 1 Q5a II-176 Cl SO₂Me —CH═CH₂ 1 Q6a II-177 Cl SO₂Me —CH₂CH═CH₂ 1 Q1a 63-68 II-178 Cl SO₂Me —CH₂CH═CH₂ 1 Q2 II-179 Cl SO₂Me —CH₂CH═CH₂ 1 Q3a II-180 Cl SO₂Me —CH₂CH═CH₂ 1 Q5a II-181 Cl SO₂Me Ph 1 Q1a II-182 Cl SO₂Me 4-F-Ph 1 Q1a II-183 Cl SO₂Me 2-Cl-Ph 1 Q1a 84-90 II-184 Cl SO₂Me 3-Et-Ph 1 Q II-185 Cl SO₂Me 4-NO₂-Ph 1 Q1a II-186 Cl SO₂Me CH₂CH₂F 1 Q1a II-187 Cl SO₂Me CH₂CH₂F 1 Q2 II-188 Cl SO₂Me CH₂CH₂F 1 Q3a II-189 Cl SO₂Me CH₂CH₂F 1 Q5a II-190 Cl SO₂Me CH₂CH₂Cl 1 Q1a II-191 Cl SO₂Me CH₂CH₂Cl 1 Q2 II-192 Cl SO₂Me CH₂CH₂Cl 1 Q3a II-193 Cl SO₂Me CH₂CH₂Cl 1 Q5a II-194 Cl SO₂Me CH₂CF₃ 1 Q1a 82-87 II-195 Cl SO₂Me CH₂CF₃ 1 Q1b II-196 Cl SO₂Me CH₂CF₃ 1 Q1c II-197 Cl SO₂Me CH₂CF₃ 1 Q2 II-198 Cl SO₂Me CH₂CF₃ 1 Q3a II-199 Cl SO₂Me CH₂CF₃ 1 Q4a II-200 Cl SO₂Me CH₂CF₃ 1 Q4b II-201 Cl SO₂Me CH₂CF₃ 1 Q5a II-202 Cl SO₂Me CH₂CF₃ 1 Q6a II-203 Cl SO₂Me CH₂CF₃ 1 Q7 II-204 Cl SO₂Me CH₂CF₂CF₃ 1 Q1a II-205 Cl SO₂Me CH₂CF₂CF₃ 1 Q2 II-206 Cl SO₂Me CH₂CF₂CF₃ 1 Q3a II-207 Cl SO₂Me CH₂CH₂CH₂F 1 Q5a II-208 Cl SO₂Me CH₂CH₂CH₂F 1 Q1a II-209 Cl SO₂Me CH₂CH₂CH₂F 1 Q2 II-210 Cl SO₂Me CH₂CH₂CH₂F 1 Q3a II-211 Cl SO₂Me CH₂CH₂CH₂F 1 Q5a II-212 Cl SO₂Et Me 1 Q1a 70-74 II-213 Cl SO₂Et Me 1 Q2 II-214 Cl SO₂Et Me 1 Q3a II-215 Cl SO₂Et Me 1 Q5a II-216 Cl SO₂Et Me 1 Q6a II-217 Cl SO₂Et Me 1 Q7 II-218 Cl SO₂Et Et 1 Q1a II-219 Cl SO₂Et Et 1 Q2 II-220 Cl SO₂Et

1 Q1a II-221 Cl SO₂Et

1 Q2 II-222 Cl SO₂Et

1 Q1a II-223 Cl SO₂Et —CH═CH₂ 1 Q1a II-224 Cl SO₂Et —CH═CH₂ 1 Q2 II-225 Cl SO₂n-Pr

1 Q1a II-226 Br Br Me 1 Q1a  72-179 II-227 Br Br Me 1 Q1b II-228 Br Br Me 1 Q1c II-229 Br Br Me 1 Q2 II-230 Br Br Me 1 Q3a II-231 Br Br Me 1 Q3c II-232 Br Br Me 1 Q3f II-233 Br Br Me 1 Q4a II-234 Br Br Me 1 Q4b II-235 Br Br Me 1 Q5a II-236 Br Br Me 1 Q5e II-237 Br Br Me 1 Q6a II-238 Br Br Me 1 Q7 II-239 Br Br Et 1 Q1a II-240 Br Br Et 1 Q2 II-241 Br Br Et 1 Q3a II-242 Br Br Et 1 Q3d II-243 Br Br Et 1 Q5a II-244 Br Br n-Pr 1 Q1a II-245 Br Br n-Pr 1 Q2 II-246 Br Br i-Pr 1 Q1a II-247 Br Br i-Pr 1 Q2 II-248 Br Br

1 Q1a II-249 Br Br

1 Q1b II-250 Br Br

1 Q1c II-251 Br Br

1 Q2 II-252 Br Br

1 Q3a II-253 Br Br

1 Q4a II-254 Br Br

1 Q4b II-255 Br Br

1 Q5a II-256 Br Br

1 Q1a II-257 Br Br —CH═CH₂ 1 Q1a II-258 Br Br —CH═CH₂ 1 Q2 II-259 Br Br —CH═CH₂ 1 Q3a II-260 Br Br —CH═CH₂ 1 Q5a II-261 Br Br —CH₂CH═CH₂ 1 Q1a II-262 Br Br —CH₂CH═CH₂ 1 Q2 II-263 Br Br Ph 1 Q1a II-264 Br Br 2-Cl-Ph 1 Q1a II-265 Br Br 2-CF₃-Ph 1 Q1a II-266 Br Br CH₂CH₂F 1 Q1a II-267 Br Br CH₂CH₂F 1 Q2 II-268 Br Br CH₂CH₂Cl 1 Q1a II-269 Br Br CH₂CH₂Cl 1 Q2 II-270 Br Br CH₂CF₃ 1 Q1a II-271 Br Br CH₂CF₃ 1 Q2 II-272 Br Br CH₂CF₃ 1 Q3a II-273 Br Br CH₂CF₃ 1 Q5a II-274 Br Br CH₂CF₂CF₃ 1 Q1a II-275 Br Br CH₂CH₂CH₂F 1 Q1a II-276 Br SO₂Me Me 1 Q1a 87-90 II-277 Br SO₂Me Me 1 Q2 II-278 Br SO₂Me Et 1 Q1a II-279 Br SO₂Me

1 Q1a II-280 Br SO₂Me

1 Q1a II-281 Br SO₂Me —CH═CH₂ 1 Q1a II-282 OMe Cl Me 1 Q1a 1.6131 II-283 OMe Cl Me 1 Q1b II-284 OMe Cl Me 1 Q1c II-285 OMe Cl Me 1 Q2 II-286 OMe Cl Me 1 Q3a II-287 OMe Cl Me 1 Q4a II-288 OMe Cl Me 1 Q4b II-289 OMe Cl Me 1 Q5a II-290 OMe Cl Me 1 Q6a II-291 OMe Cl Et 1 Q1a II-292 OMe Cl Et 1 Q2 II-293 OMe Cl Et 1 Q3a II-294 OMe Cl Et 1 Q5a II-295 OMe Cl Et 1 Q7 II-296 OMe Cl n-Pr 1 Q1a II-297 OMe Cl n-Pr 1 Q2 II-298 OMe Cl i-Pr 1 Q1a II-299 OMe Cl i-Pr 1 Q2 II-300 OMe Cl

1 Q1a II-301 OMe Cl

1 Q1b II-302 OMe Cl

1 Q1c II-303 OMe Cl

1 Q2 II-304 OMe Cl

1 Q3a II-305 OMe Cl

1 Q4a II-306 OMe Cl

1 Q4b II-307 OMe Cl

1 Q5a II-308 OMe Cl

1 Q1a II-309 OMe Cl

1 Q1a II-310 OMe Cl —CH═CH₂ 1 Q1a II-311 OMe Cl —CH═CH₂ 1 Q2 II-312 OMe Cl —CH═CH₂ 1 Q3a II-313 OMe Cl —CH═CH₂ 1 Q5a II-314 OMe Cl —CH₂CH═CH₂ 1 Q1a II-315 OMe Cl —CH₂CH═CH₂ 1 Q2 II-316 OMe Cl Ph 1 Q1a II-317 OMe Cl 2-Cl-Ph 1 Q1a II-318 OMe Cl CH₂CH₂F 1 Q1a II-319 OMe Cl CH₂CH₂F 1 Q2 II-320 OMe Cl CH₂CH₂Cl 1 Q1a II-321 OMe Cl CH₂CH₂Cl 1 Q2 II-322 OMe Cl CH₂CF₃ 1 Q1a II-323 OMe Cl CH₂CF₃ 1 Q2 II-324 OMe Cl CH₂CF₃ 1 Q3a II-325 OMe Cl CH₂CF₃ 1 Q5a II-326 OMe Cl CH₂CF₂CF₃ 1 Q1a II-327 OMe Cl CH₂CH₂CH₂F 1 Q1a II-328 OCHF₂ Cl Me 1 Q1a II-329 OCHF₂ Cl Me 1 Q2 II-330 OCHF₂ Cl Me 1 Q3a II-331 OCHF₂ Cl Et 1 Q1a II-332 OCHF₂ Cl

1 Q1a II-333 OCHF₂ Cl —CH═CH₂ 1 Q1a II-334 OCH₂CF₃ Cl Me 1 Q1a II-335 OCH₂CF₃ Cl Me 1 Q2 II-336 OCH₂CF₃ Cl Et 1 Q1a II-337 SMe Cl Me 1 Q1a II-338 SMe Cl Me 1 Q2 II-339 SMe Cl Et 1 Q1a II-340 SMe Cl

1 Q1a II-341 SMe Cl —CH═CH₂ 1 Q1a II-342 SMe SMe Me 1 Q1a II-343 SMe SMe Me 1 Q2 II-344 SMe SMe Et 1 Q1a II-345 SMe SMe

1 Q1a II-346 SMe SMe —CH═CH₂ 1 Q1a II-347 SO₂Me Cl Me 1 Q1a II-348 SO₂Me Cl Me 1 Q2 II-349 SO₂Me Cl Et 1 Q1a II-350 SO₂Me Cl

1 Q1a II-351 SO₂Me Cl —CH═CH₂ 1 Q1a II-352 SO₂Me SO₂Me Me 1 Q1a II-353 SO₂Me SO₂Me Me 1 Q2 II-354 SO₂Me SO₂Me Et 1 Q1a II-355 SO₂Me SO₂Me

1 Q1a II-356 SO₂Me SO₂Me —CH═CH₂ 1 Q1a II-357 Me SO₂Me Me 1 Q1a 69-71 II-358 Me SO₂Me Me 2 Q1a II-359 Me SO₂Me Me 1 Q1b II-360 Me SO₂Me Me 1 Q1c II-361 Me SO₂Me Me 1 Q2 II-362 Me SO₂Me Me 1 Q3a II-363 Me SO₂Me Me 1 Q3c II-364 Me SO₂Me Me 1 Q3d II-365 Me SO₂Me Me 1 Q4a II-366 Me SO₂Me Me 1 Q4b II-367 Me SO₂Me Me 1 Q5a II-368 Me SO₂Me Me 1 Q5c II-369 Me SO₂Me Me 1 Q6a II-370 Me SO₂Me Me 1 Q7 II-371 Me SO₂Me Et 1 Q1a II-372 Me SO₂Me Et 1 Q2 II-373 Me SO₂Me Et 1 Q3a II-374 Me SO₂Me Et 1 Q3b II-375 Me SO₂Me Et 1 Q5a II-376 Me SO₂Me n-Pr 1 Q1a II-377 Me SO₂Me n-Pr 1 Q2 II-378 Me SO₂Me i-Pr 1 Q1a II-379 Me SO₂Me i-Pr 1 Q2 II-380 Me SO₂Me

1 Q1a II-381 Me SO₂Me

1 Q1b II-382 Me SO₂Me

1 Q1c II-383 Me SO₂Me

1 Q2 II-384 Me SO₂Me

1 Q3a II-385 Me SO₂Me

1 Q4a II-386 Me SO₂Me

1 Q4b II-387 Me SO₂Me

1 Q5a II-388 Me SO₂Me

1 Q1a II-389 Me SO₂Me

1 Q1a II-390 Me SO₂Me

1 Q1a II-391 Me SO₂Me —CH═CH₂ 1 Q1a II-392 Me SO₂Me —CH═CH₂ 1 Q2 II-393 Me SO₂Me —CH═CH₂ 1 Q3a II-394 Me SO₂Me —CH═CH₂ 1 Q5a II-395 Me SO₂Me —CH₂CH═CH₂ 1 Q1a II-396 Me SO₂Me —CH₂CH═CH₂ 1 Q2 II-397 Me SO₂Me Ph 1 Q1a II-398 Me SO₂Me 2-Cl-Ph 1 Q1a II-399 Me SO₂Me 4-NO₂-Ph 1 Q1a II-400 Me SO₂Me CH₂CH₂F 1 Q1a II-401 Me SO₂Me CH₂CH₂F 1 Q2 II-402 Me SO₂Me CH₂CH₂Cl 1 Q1a II-403 Me SO₂Me CH₂CH₂Cl 1 Q2 II-404 Me SO₂Me CH₂CF₃ 1 Q1a II-405 Me SO₂Me CH₂CF₃ 1 Q2 II-406 Me SO₂Me CH₂CF₃ 1 Q3a II-407 Me SO₂Me CH₂CF₃ 1 Q5a II-408 Me SO₂Me CH₂CF₂CF₃ 1 Q1a II-409 Me SO₂Me CH₂CH₂CH₂F 1 Q1a II-410 CN SO₂Me Me 1 Q1a 54-60 II-411 CN SO₂Me Me 1 Q2 II-412 CN SO₂Me Me 1 Q3a II-413 CN SO₂Me Et 1 Q1a II-414 CN SO₂Me

1 Q1a II-415 CN SO₂Me

1 Q5a II-416 Cl SEt Me 1 Q1a II-417 Cl SO₂Me Me 1 Q3g II-418 Cl SO₂Me Me 1 Q4c II-419 Cl SO₂Me Me 1 Q4d II-420 Cl SO₂Me Me 1 Q6b II-421 Cl SO₂Me n-Bu 1 Q1a II-422 Cl SO₂Me n-Hex 1 Q1a II-423 Cl SO₂Me —CH₂CH═CHCH₃ 1 Q1a II-424 Cl SO₂Me —(CH₂)₄CH═CH₂ 1 Q1a II-425 Cl SO₂Me 4-(n-Pr)-Ph 1 Q1a II-426 Cl SO₂Me 4-(CH₂CH₂Cl)-Ph 1 Q1a II-427 Cl SO₂Me —(CH₂)₄Cl 1 Q1a II-428 OEt Cl Me 1 Q1a II-429 OSO₂Me Cl Me 1 Q1a II-430 OSO₂Et Cl Me 1 Q1a II-431 Et SO₂Me Me 1 Q1a II-432 Cl SO₂Me Me 1 Q3h II-433 Cl SO₂Me Me 1 Q3i 128-131 II-434 Cl SO₂Me Me 1 Q3j II-435 Cl SO₂Me Me 1 Q3d 85-91 II-436 Cl SO₂Me Me 1 Q3k II-437 Cl SO₂Me Me 1 Q3l II-438 Cl SO₂Me Me 1 Q3m II-439 Cl SO₂Me Me 1 Q3n II-440 Cl SO₂Me Me 1 Q3o II-441 Cl SO₂Me Me 1 Q3p II-442 Cl SO₂Me Me 1 Q3q II-443 Cl SO₂Me Me 1 Q3r II-444 Cl SO₂Me Me 1 Q3s II-445 Cl SO₂Me Me 1 Q3t II-446 Cl SO₂Me Me 1 Q3u II-447 Cl SO₂Me Me 1 Q3v II-448 Cl SO₂Me Me 1 Q3w II-449 Cl SO₂Me Me 1 Q3b II-450 Cl SO₂Me Me 1 Q3x II-451 Cl SO₂Me Me 1 Q3y 208-209 II-452 Cl SO₂Me Me 1 Q3f II-453 Cl SO₂Me Me 1 Q3z II-454 Cl SO₂Me Me 1 Q3za II-455 Cl SO₂Me Me 1 Q3zb II-456 Cl SO₂Me Me 1 Q3zc II-457 Cl SO₂Me Me 1 Q3zd

[0420] TABLE 3

Com- pound melting point No. X Y R n Q (mp) or n_(D) ²⁰ III-1  H H Me 1 Q1a III-2  H H Me 2 Q1a III-3  H H Me 1 Q2 III-4  H OMe Me 1 Q1a III-5  H NO₂ Me 1 Q1a III-6  F H Me 1 Q1a III-7  F H Me 1 Q2 III-8  F H Et 1 Q1a III-9  F H

1 Q1a III-10  F H —CH═CH₂ 1 Q1a Ill-11  Cl H Me 1 Q1a III-12  Cl H Me 2 Q1a III-13  Cl H Me 1 Q2 III-14  Cl H Me 1 Q3a III-15  Cl H Me 1 Q5a III-16  Cl H Me 1 Q6a III-17  Cl H Et 1 Q1a III-18  Cl H

1 Q1a III-19  Cl H —CH═CH₂ 1 Q1a III-20  Br H Me 1 Q1a III-21  Br H Me 1 Q2 III-22  Br H Me 1 Q3a III-23  Br H Me 1 Q5a III-24  Br H Me 1 Q7 III-25  Br H Et 1 Q1 III-26  Br H

1 Q1a III-27  Br H —CH═CH₂ 1 Q1a III-28  I H Me 1 Q1a III-29  I H Me 1 Q2 III-30  I H Me 1 Q3a III-31  I H Me 1 Q5a III-32  I H Me 1 Q6a III-33  I H Et 1 Q1a III-34  I H

1 Q1a III-35  I H —CH═CH₂ 1 Q1a III-36  CF₃ H Me 1 Q1a III-37  CF₃ H Me 1 Q2 III-38  CF₃ H Me 1 Q3a III-39  CF₃ H Me 1 Q5a III-40  CF₃ H Me 1 Q6a III-41  CF₃ H Et 1 Q1a III-42  CF₃ H

1 Q1a III-43  CF₃ H —CH═CH₂ 1 Q1a III-44  OMe H Me 1 Q1a III-45  OMe H Me 1 Q2 III-46  OMe H Me 1 Q3a III-47  OMe H Me 1 Q5a III-48  OMe H Et 1 Q1a III-49  OMe H

1 Q1a III-50  OMe H —CH═CH₂ 1 Q1a III-51  OSO₂Me H Me 1 Q1a III-52  OSO₂Me H Me 1 Q2 III-53  OSO₂Me H Me 1 Q3a III-54  OSO₂Me H Me 1 Q5a III-55  OSO₂Me H Et 1 Q1a III-56  OSO₂Me H

1 Q1a III-57  OSO₂Me H —CH═CH₂ 1 Q1a III-58  SMe H Me 1 Q1a III-59  SMe H Me 1 Q III-60  SMe H Me 1 Q3a III-61  SMe H Et 1 Q1a III-62  SMe H

1 Q1a III-63  SMe H —CH═CH₂ 1 Q1a III-64  OSO₂Me H Me 1 Q1a III-65  OSO₂Me H Me 1 Q2 III-66  OSO₂Me H Me 1 Q3a III-67  OSO₂Me H Me 1 Q5a III-68  OSO₂Me H Et 1 Q1a III-69  OSO₂Me H

1 Q1a III-70  OSO₂Me H —CH═CH₂ 1 Q1a III-71  NO₂ H Me 1 Q1a 82-87 III-72  NO₂ H Me 2 Q1a III-73  NO₂ H Me 1 Q1b III-74  NO₂ H Me 1 Q1c III-75  NO₂ H Me 1 Q2 III-76  NO₂ H Me 1 Q3a III-77  NO₂ H Me 1 Q4a III-78  NO₂ H Me 1 Q4b III-79  NO₂ H Me 1 Q5a III-80  NO₂ H Me 1 Q6a III-81  NO₂ H Me 1 Q7 III-82  NO₂ H Et 1 Q1a III-83  NO₂ H Et 1 Q2 III-84  NO₂ H Et 1 Q3a III-85  NO₂ H Et 1 Q5a III-86  NO₂ H Et 1 Q6a III-87  NO₂ H n-Pr 1 Q1a III-88  NO₂ H n-Pr 1 Q2 III-89  NO₂ H i-Pr 1 Q1a III-90  NO₂ H I-Pr 1 Q2 III-91  NO₂ H

1 Q1a III-92  NO₂ H

1 Q2 III-93  NO₂ H

1 Q3 III-94  NO₂ H

1 Q5a III-95  NO₂ H

1 Q1a III-96  NO₂ H —CH═CH₂ 1 Q1a III-97  NO₂ H —CH═CH₂ 1 Q2 III-98  NO₂ H —CH═CH₂ 1 Q3a III-99  NO₂ H —CH═CH₂ 1 Q5a III-100 NO₂ H —CH₂CH═CH₂ 1 Q1a III-101 NO₂ H Ph 1 Q1a III-102 NO₂ H 2-Cl-Ph 1 Q1a III-103 NO₂ H CH₂CH₂F 1 Q1a III-104 NO₂ H CH₂CH₂Cl 1 Q1a III-105 NO₂ H CH₂CF₃ 1 Q1a III-106 NO₂ H CH₂CH₂F 1 Q1a III-107 NO₂ H CH₂CF₂CF₃ 1 Q1a III-108 NO₂ H CH₂CH₂CH₂F 1 Q1a III-109 CN H Me 1 Q1a III-110 CN H Me 1 Q2 Ill-111 CN H Me 1 Q3a III-112 CN H Me 1 Q5a III-113 CN H Et 1 Q1a III-114 CN H

1 Q1a III-115 CN H —CH═CH₂ 1 Q1a

Synthesis Example 4

[0421]

[0422] 2-Chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoic acid (0.77 g) and thionyl chloride (0.49 g) were added to 1,2-dichloroethane (30 ml) and the mixture was, after addition of 2 drops of N,N-dimethylformamide, refluxed for 3 hours. After cooling, the residue obtained by distilling off the solvent was dissolved in dichloromethane (10 ml) and the mixture was added dropwise to a solution of 1,3-cyclohexanedione (0.28 g) and triethylamine (0.28 g) in dichloromethane (10 ml) at 5° C. and stirred at room temperature for 6 hours. After the reaction the mixture was extracted with dichloromethane (100 ml), washed with diluted hydrochloric acid and an aqueous dolution of sodium hydrogen carbonate, and dried with anhydrous magnesium sulfate. The residue obtained by distilling off the dichloromethane was purified by silica gel column chromatography (eluant:ethyl acetate:hexane=3:7) to obtain the objective 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate (0.83 g). mp: 122-123° C.

Synthesis Example 5

[0423]

[0424] To a solution of methyl 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-meth-ylsulfonylbenzoate (0.83 g) in dioxane (15 ml), a 10N aqueous solution of sodium hydroxide (1.0 ml) and water (2 ml) were added and the mixture was stirred at room temperature for 3 hours. Water (30 ml) is added. Then, after concentration under reduced pressure, a 10N aqueous solution of sodium hydroxide (1.0 ml) was added to the concentrate and the concentrate is washed with ethyl acetate (100 ml). The aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. Ethyl acetate was distilled off to obtain the objected 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methyl-sulfonylbenzoic acid (0.80 g). mp: 193-195° C.

Synthesis Example 6

[0425]

[0426] 1-Ethyl-5-mercaptotetrazole (0.31 g) and methyl 3-bromomethyl-2-chloro-4-methyl-sulfonylbenzoate (0.80 g) were suspended in acetonitrile (20 ml) and the suspension was, after addition of potassium carbonate (0.32 g), refluxed for 3 hours. After addition of cold water upon the completion of the reaction, the mixture was extracted with ethyl acetate (100 ml) and dried with anhydrous magnesium sulfate. The residue obtained by distilling off the ethyl acetate was recrystallized from dichloromethane-hexane to obtain the objected methyl 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate (0.88 g), mp: 109-1 10° C.

Test Example 1

[0427] Test for Herbicidal Effect Against Paddy Field Weeds

[0428] Preparation of a Formulation of the Active Compound Carrier: Acetone 5 parts by weight Emulsifier: Benzyloxypolyglycolether 1 part by weight

[0429] A formulation of the active substance is obtained as an emulsion by mixing 1 part by weight of the active compound with the above-mentioned amount of carrier and emulsifier. A prescribed amount of the formulation is diluted with water.

[0430] Test Method

[0431] In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare) of 2.5 leafstage (15 cm tall) were planted in a 500 cm² pot filled with paddy field soil. Then seeds or tubers of smallflower, bulrush, monochoria, broad-leaved weeds (common false pimpernel, Indian toothcup, long stemmed water wort, Dopatrium junceum Hammilt etc.) and Japanese ribbon wapato were inoculated and water was poured to a depth of about 2-3 cm.

[0432] 5 Days after the rice transplantation a formulation of each active compound prepared according to the aforementioned preparation method was applied to the surface of the water. The herbicidal effect was examined after 3 weeks from the treatment during which period the water depth of 3 cm was maintained. The herbicidal effect was rated as 100% in the case of complete extiinction and as 0% in the case of no herbicidal effect.

[0433] As a result, the compounds No. H-18, II-117, II-122, II-131, II-194, II-212 and III-71 showed at the application rate of 0.25 kg/ha a herbicidal effect of more than 90% against paddy field weeds and showed safety to the transplanted paddy rice.

Test Example 2

[0434] Test of Pre-Emergence Soil Treatment Against Field Weeds

[0435] Test Method

[0436] In a greenhouse, on the surface layer of a 120 cm² pot filled with field soil, and then seeds of barnyardgrass, foxtail, common amaranth and knotweed were sown and covered with soil. The prescribed amount of chemicals prepared in the same manner as in the above-mentioned Test Example 1 was spread uniformly on the soil surface layer of each test pot. The herbicidal effect was examined after 4 weeks from the treatment.

[0437] Effects:

[0438] The compounds No. II-117, II-122 and II-194 showed at application rate of 2.0 kg/ha herbicidal activities of more than 90% against objective weeds (barnyardgrass, foxtail, common amaranth and knotweed).

Test Example 3

[0439] Test of Post-Emergence Foliage Treatment Against Field Weeds

[0440] Test Method

[0441] In a greenhouse, seeds of barnyardgrass, foxtail, common amaranth and knotweed were sown in 120 cm² pots filled with field soil and covered with soil. After 10 days after the sowing and soil covering (weeds were 2-leafstage in average) the prescribed amount of chemicals prepared in the same manner as in the above-mentioned Test Example 1 was spread uniformly on the foliage of the test plants in each test pot. The herbicidal effect was examined after 3 weeks from-the treatment.

[0442] Results:

[0443] The compounds No. II-18, II-117, II-122, II-131, II-194, II-212 and II-276 showed at the chemical amount of 2.0 kg/ha herbicidal activities of more than 90% against barnyardgrass, foxtail, common amaranth and knotweed.

Test Example 4

[0444] Test for Synergistic Action by Foliar Spray Application

[0445] Preparation of the Test Solution Carrier: acetone, 5 parts by weight Emulsifier: benzyloxypolyglycol ether, 1 parts by weight

[0446] One part of an active compound and the above amounts of carrier and emulsifier are mixed to obtain a formulation of the active substance as an emulsion. A prescribed amount of this formulation is diluted with water to prepare testing solutions.

[0447] Test Method

[0448] In a greenhouse, paddy soil was filled in pots (250 cm²), and seeds of weed (barnyardgrass, bulrush, monochoria and falspimernel) were inoculated in the surface layer of the soil in the pots under wet conditions and covered with soil. All of the weed species were individually inoculated in each pot. Each pot was watered to 2 cm in depth. When the weeds grew up to 1.5-2.2 leaf stage (or pair), a predetermined amount of the compound as a testing solution prepared in the above was applied to the weeds in pots by foliar spray after draining the water in the pot. On the day following the application, the pots were irrigated again to 2 cm of water depth. The herbicidal effect was evaluated at 4 weeks after the application on a scale of 0(not active) to 100(complete damage).

[0449] Test results of test example 4 are shown in Table 4.

Test Example 5

[0450] Test for Synergistic Action by Water Sureface Application

[0451] Test Method

[0452] In a greenhouse, paddy soil was filled in pots (250 cm²), and seeds of weed (barnyardgrass, bulrush, monochoria, falspimernel, indian toothcup, waterwort and flatstage) were inoculated in the surface layer of the soil in the pots under wet conditions and covered with soil. All of the weed species were individually inoculated in each pot. Each pot was watered to 2 cm in depth and the depth was kept during the test period. When the weeds grew up to 1.5-2.2 leaf stage (or pair), a predetermined amount of the compound as a testing solution prepared in the same manner as the above-mentioned Test Example 4 was applied to the pots by water surface treatment method. The herbicidal effect was evaluated at 4 weeks after the application on the same scale as in the test method of Test Example 4.

[0453] Test results of test example 5 are shown in Table 5.

[0454] Synergistic action of Test Example 4 and Test Example 5 were evaluated by Colby's equation. ${{Colby}:\quad E} = {X + \left\lbrack {Y \times \frac{\left( {100 - X} \right)}{100}} \right\rbrack}$

[0455] E: expected herbicidal activity at p+q g/ha

[0456] X: the percentage of herbicidal activity at p g/ha

[0457] Y: the percentage of herbicidal activity at q g/ha.

[0458] The following abbreviations are used in Table 4 and Table 5: CYPSE represents Cyperus serotinus (flatstage), ECHSS represents Echinochloa spp. (barnyardgrass), ELTTP reprerstnts Elatine triandra (waterwort), LIDPY represents Lindernia pyridaria (flasepimpernel), MOOVP represents Monochoria vaginalis (monochoria), ROTIN represents Rotala indica (indian toothcup),

[0459] Compounds (1) in Table 4 and Table 5 are listed by the compound numbers previously used in Tables 1, 2 and 3.

[0460] In Table 4 and Table 5 other known herbicides are represented by the capital letters as shown in the following list:

[0461] A: 4-(2-chlorophenyl)-N-cyclohexyl-N-ethyl-4,5-dihydro-5-oxo-1H-tetrazole-1-carboxamide (fentrazamide),

[0462] B: 3,′4′-dichloropropionanilide (propanil),

[0463] C: N,N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazole-1-carboxamide (cafenstrole),

[0464] D: 3-[1-(3,5-dichlorophenyl)-1-methylethyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (oxaziclomefone),

[0465] E: 2-chloro-2′,6′-diethyl-N-(2-propoxyethyl) acetamide (pretilachlor),

[0466] F: 2-(1,3-benzothiazol-2-yloxy)-N-methylacetanilide (mefenacet),

[0467] G: (RS)-2-[2-(3-chlorophenyl)2,3-epoxypropyl]-2-ethylindan-1,3-dione (indanofan).

[0468] TABLE 4 Herbicidal efficacy (%) by foliar spray application Herbicidal efficacy (%) known compound(1) + Expected activ- Test compound(1) herbicide known herbicide ity E according plant (g a.i./ha) (g a.i./ha) (g a.i./ha) to Colby (%) 1^(st) run: II-131 A II-131 + A II-131 + A (125) (135) (125 + 135) SCPSS 70 60 90 88 MOOVP 70 60 95 88 LIDPY 50 50 80 75 2^(nd) run: II-131 B II-131 + B II-131 + B (125) (750) (125 + 750) ECHSS 40 30 80 58 SCPSS 70 10 80 73 MOOVP 70 30 90 79 LIDPY 50 40 80 70

[0469] TABLE 5 Herbicidal efficacy (%) by water surface application Herbicidal efficacy (%) Expected known compound(1) + activity Test compound(1) herbicide known herbicide E According to plant (g a.i./ha) (g a.i./ha) (g a.i./ha) Colby (%) 1^(st) run: II-117 A II-117 + A II-117 + A (75) (100) (75 + 100) LIDPY 75 50 100    87.5 ROTIN 50 70 95 85 ELTTP 50 80 95 90 2^(nd) run: II-117 C II-117 + C II-117 + C (75) (100) (75 + 100) LIDPY 70 60 90 88 3^(rd) run: II-122 D II-122 + D II-122 + D (60) (40) (60 + 40) ECHSS  0 80 85 80 SCPSS 60 30 80 72 LIDPY 70 40 90 82 4^(th) run: II-18 E II-18 + E II-18 + E (60) (300) (60 + 300) MOOVP 80 60 100  92 LIDPY 60 60 95 84 CYPSE 50 40 80 70 5^(th) run: III-71 F III-71 + F III-71 + F (125) (500) (125 + 500) LIDPY 80 40 95 88 ROTIN 70 40 90 82 run6: III-71 G III-71 + G III-71 + G (125) (75) (125 + 75) LIDPY 80 60 98 92 ROTIN 70 60 95 88

Test Example 6

[0470] Test for Safening Action on Rice by Water Surface Application

[0471] Test method

[0472] In a greenhouse, paddy soil was filled in pots (1,000 cm²), and seeds of rice (cv. Nipponbare) were sown in the surface layer of the soil in the pots under wet conditions. 7 days after seeding, at the one leaf stage of the rice seedlings, the pots were watered to 3 cm in depth and the depth was kept during the test period. When the rice seedlings grew up to 1.5 leaf stage during the 9 days after seeding, a predetermined amount of the compound as a testing solution prepared in the same manner as the above-mentioned Test Example 4 was applied to the pots by water surface treatment method. The phytotoxicity to rice seedlings was evaluated at 3 weeks after the application on a scale of 0 (no damage) to 100 (complete deth).

[0473] Test result of test example 6 are shown in Table 6.

[0474] Safening action of Test Example 6 were evaluated by Colby's equation. ${{Colby}:\quad E} = {X + \left\lbrack {Y \times \frac{\left( {100 - X} \right)}{100}} \right\rbrack}$

[0475] E: expected phytotoxicity at p+q g/ha

[0476] X: expected phytotoxicity at p g/ha

[0477] Y: expected phytotoxicity at q g/ha

[0478] Compounds (1) in Table 6 are listed by by the compound numbers previously uesd in Tables 1, 2 and 3.

[0479] In Table 6 the known safeners are represented by the capital letters as shown in the following list:

[0480] a: N,N-diallyl-2,2-dichloroacetamide (dichlormid),

[0481] b: 4,6-dichloro-2-phenylpyrimidine (fenclorin),

[0482] c: diethyl (RS)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylate (mefenpyr-diethyl),

[0483] d: N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),

[0484] e: 2-(dichloroacetyl)-2,2,5-trimethyl-oxazolidine (R-29148),

[0485] f: 1H,3H-naphtho [1,8-cd]pyran-1,3-dione(naphthalic anhydride). TABLE 6 Safening efficacy (%) by water surface application Expected compound (1) + phytotoxcity (E) compound (1) Phytotoxicity safener phytotoxicity safener phytotoxicity according to (g a.i./ha) (%) (g a.i./ha) (%) (g a.i./ha) (%) Colby (%) II-276 40 a (200) 0 II-276 + a 5 40 (400) (400 + 200) b (400) 0 II-276 + b 20 40 (400 + 400) c (400) 20 II-276 + c 25 52 (400 + 400) II-131 40 d (400) 0 II-131 + d 10 40 (400) (400 + 400) b (400) 0 II-131 + b 15 40 (400 + 200) e (200) 0 II-131 + e 20 40 (400 + 200) II-122 30 d (400) 0 II-122 + d 10 30 (600) (600 + 400) a (200) 0 II-122 + a 10 30 (600 + 200) b (400) 0 II-122 + b 5 30 (600 + 400) f (400) 0 II-122 + f 0 30 (600 + 400) II-117 60 d (400) 0 II-117 + d 30 60 (400) (400 + 400) a (200) 0 II-117 + a 40 60 (400 + 200) f (400) 0 II-117 + f 30 60 (400 + 400) III-71 30 a (200) 0 III-71 + a 10 30 (600) (600 + 200) c (400) 20 III-71 + c 20 44 (600 + 400) II-194 50 d (400) 0 II-194 + d 25 50 (400) (400 + 400) b (400) 0 II-194 + b 30 50 (400 + 400) f (400) 0 II-194 + f 20 50 (400 + 400)

Formulation Example 1 (Granule)

[0486] To a mixture of the compound No. II-18 of the present invention (2.5 parts), bentonite (montmorillonite) (30 parts), talc (65.5 parts) and ligninsulphonate salt (2 parts), water (25 parts) is added. The mixture is well kneaded, made in granules of 10-40 mesh by an extrusion granulator and dried at 40-50° C. to obtain a granule.

Formulation Example 2 (Granule)

[0487] Clay mineral particles having particle size distribution of 0.2-2 mm (95 parts) are put in a rotary mixer. While rotating it, the compound No. II-117 of the present invention (5 parts) is sprayed together with a liquid diluent into the mixer wetted uniformly and dried at 40-50° C. to obtain granules.

Formulation Example 3 (Emulsifiable Concentrate)

[0488] The compound No. II-122 of the present invention (30 parts), xylene (5 parts), poly-oxyethylenealkyl phenyl ether (8 parts) and calcium alkylbenzenesulfonate (7 parts) are mixed and stirred to obtain an emulsion.

Formulation Example 4 (Wettable Powder)

[0489] The compound No. II-194 of the present invention (15 parts), a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5) (80 parts), sodium alkylbenzenesulfonate (2 parts) and sodium alkylnaphthalene-sulfonate-formalin-polymer (3 parts) are mixed in powder form and made into a wettable powder.

Formulation Example 5 (Water-Dispersible Granule)

[0490] The compound No. II-18 of the present invention (20 parts), sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) are well mixed, added with water, extruded using a 0.3 mm screen and dried to obtain a water-dispersible granules. 

1. A compound of the formula (I)

wherein R¹ represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, C₁₋₂ haloalkoxy, methylthio, ethylthio, C₁₋₃ alkylsulfonyl, methyl-sulfonyloxy, ethylsulfonyloxy, nitro or cyano, R² represents C₁₋₆ alkyl, C₃₋₆ cycloalkyl which may be optionally substituted with halogen or C₁₋₃ alkyl, C₁₋₄ haloalkyl, C₂₋₆ alkenyl, or phenyl which may be optionally substituted with halogen, C₁₋₃ alkyl, C₁₋₂ haloalkyl or nitro, m represents 0, 1 or 2, the two R¹ substituents may be identical or different, in case m represents 2, n represents 1 or,2, Q represents one of the following groups

wherein R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each represents a hydrogen atom or methyl, R⁹ represents a hydrogen atom, halogen, C₁₋₃ alkyl, halomethyl, methoxy or nitro, R¹⁰ represents C₁₋₆ alkyl, R¹¹ represents halogen, and k represents 1 or
 2. 2. A compound of the formula (I) according to claim 1 wherein R¹ represents fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, C₁₋₂ haloalkoxy, methylthio, ethylthio, methyl-sulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano, R² represents C₁₋₃ alkyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl or ethyl, C₁₋₃ haloalkyl, C₂₋₄ alkenyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, ethyl, trifluoromethyl or nitro, m represents 1 or 2, the two R¹ substituents may be identical or different, in case m represents 2, n represents 1 or 2, Q represents one of the following groups

wherein R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each represents a hydrogen atom or methyl, R⁹ represents a hydrogen atom, fluoro, chloro, methyl, ethyl or trifluoro-methyl R¹⁰ represents methyl or ethyl, R¹¹ represents chloro or bromo, and k represents
 1. 3. The compounds of the formula (I) according to in claim 1 wherein R¹ represents chloro, bromo, methyl or methylsulfonyl, R² represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl, m represents 2, and in this case the two R¹ substituents are bond respectively to the 2-position and 4-position of a benzene ring and the two R¹ substituents may be identical or different, n represents 1, the group

bonds to the 3-position of the benzene ring, and Q represents one of the following groups


4. A process for the preparation of the compounds of claim 1 characterized in that a) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-1) or (Q-2): compounds of the formula (II)

wherein R¹, R², m and n have the same definition as mentioned in claim 1, and T¹ represents one of the following groups

wherein R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as mentioned in claim 1, are reacted to a rearrangement in the presence of inert solvents, and if appropriate, in the presence of a base and cyanide, and if appropriate, in the presence of a phase-transfer catalyst, or b) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-6) or (Q-7) and R¹¹ in said groups represents chloro or bromo: compounds of the formula (Ib)

wherein R¹, R², m and n have the same definition as mentioned in claim 1, and Q_(b) represents one of the following groups

wherein R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as mentioned in claim 1, are reacted with a halogenating agent in the presence of inert solvents, or c) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-3), (Q-4) or (Q-5): compounds of the formula (Ic)

wherein R¹, R², m and n have the same definition as mentioned in claim 1, and Q_(c) represents one of the following groups

wherein R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as mentioned in claim 1, R^(11c) represents chloro or bromo, are reacted with compounds of the formula (III) R¹²—SH   (III) wherein R¹² represents the group

R¹⁰ wherein R⁹, R¹⁰ and k have the same definition as mentioned in claim 1, in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent.
 5. A herbicidal composition, characterized in that it contains at least one compound according to claim
 1. 6. A method for combating weeds, characterized in that a compound according to claim 1 is allowed to act on weeds and/or their habitat.
 7. Use of a compound according to claim 1 for combating weeds.
 8. A process for the preparation of herbicidal compositions, characterized in that a compound according to claim 1 is mixed with extenders and/or surface active agents.
 9. A compound represented by the formula (X)

wherein R¹, R², m and n have the same definition as mentioned in claim 1, W represents halogen, hydroxy, C₁₋₄ alkoxy or one of the following groups

R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as mentioned in claim
 1. 10. A Herbicidal composition, characterized in that it contains an acitive substance combination comprising one tetrazole derivative of the formula (I) according to claim 1 and at least one known active ingredient selected from the group consisting of acetamide type herbicides, amide type herbicides, benzofuran type herbicides, indanedione type herbicides, pyrazole type herbicides, oxazinone type herbicides, sulfonylurea type herbicides, thio-carbamate type herbicides, triazine type herbicides, triazole type herbicides, quinoline type herbicides, isoxazole type herbicides, dithiophosphate type herbicides, oxyacetamide type herbicides, tetrazolinone type herbicides, dicarboxyimide type herbicides, trione type herbicides, phenoxypropinate type herbicides, benzoic acid type herbicides, diphenylether type herbicides, pyridinedicarbothioate type herbicides, phenoxy type herbicides, urea type herbicides, naphthalenedione type herbicides and isoxazolidinone type herbicides.
 11. A herbicidal composition, characterized in that it contains an active substance combination comprising one tetrazole derivative of formula (I) according to claim 1 and at least one known safener selected from the group consisting of AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flurazole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), Mefenpyr (-diethyl), MG-191, Naphthalic anhydride, Oxabetrinil, PPG-1292, R-29148.
 12. A Herbicidal composition, characterized in that they contain an active substance combination comprising one tetrazole derivative of the formula (I) according to claim 1 together with at least one active ingredient selected from the group consisting of acetamide type herbicides, amide type herbicides, benzofuran type herbicides, indanedione type herbicides, pyrazole type herbicides, oxazinone type herbicides, sulfonylurea type herbicides, thio-carbamate type herbicides, triazine type herbicides, triazole type herbicides, quinoline type herbicides, isoxazole type herbicides, dithiophosphate type herbicides, oxyacetamide type herbicides, tetrazolinone type herbicides, di-carboxyimide type herbicides, trione type herbicides, phenoxypropinate type herbicides, benzoic acid type herbicides, diphenylether type herbicides, pyridinedicarbothioate type herbicides, phenoxy type herbicides, urea type herbicides, naphthalenedione type herbicides and isoxazolidinone type herbicides, and at least one known safener selected from the group consisting of AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flur-azole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), Mefenpyr (-diethyl), MG-191, Naphthalic anhydride, Oxabetrinil, PPG-1292, R-29148.
 13. A process for combating weeds, characterized in that an active substance combination according to any of claims 10, 11 or 12 is allowed to act on the weeds and/or their habitat.
 14. Use of an active substance combination according to any of claims 10, 11 or 12 for combating weeds.
 15. A process for the preparation of a herbicidal composition, characterized in that an active substance combination according to any of claims 10, 11 or 12 is mixed with extenders and/or surface-active agents. 